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EP1303583B1 - Reinigungsverfahren harter oberflächen - Google Patents

Reinigungsverfahren harter oberflächen Download PDF

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Publication number
EP1303583B1
EP1303583B1 EP01954112A EP01954112A EP1303583B1 EP 1303583 B1 EP1303583 B1 EP 1303583B1 EP 01954112 A EP01954112 A EP 01954112A EP 01954112 A EP01954112 A EP 01954112A EP 1303583 B1 EP1303583 B1 EP 1303583B1
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EP
European Patent Office
Prior art keywords
composition
hard surface
cleaning
reaction
change
Prior art date
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Revoked
Application number
EP01954112A
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English (en)
French (fr)
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EP1303583A1 (de
Inventor
Malcolm Tom Mckechnie
Angus Lang
Michael Alexander Priestnall
Jonathan Bamforth
Matthew Davies
Stephen Keith Scott
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Reckitt Benckiser UK Ltd
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Reckitt Benckiser UK Ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0056—Lavatory cleansing blocks
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • This invention relates to a method of cleaning a hard surface which is subject to deposition by limescale.
  • Bathroom cleaners are mainly acidic compositions, intended to combat calcium deposits.
  • kitchen cleaners are mainly alkaline compositions, intended to combat grease deposits.
  • an alkaline composition is required; and in which for kitchen cleaning, an acidic cleaning composition is required.
  • the customer has to decide whether to purchase a plethora of different products for different cleaning tasks, or whether to compromise. It would be good to have a single composition which was able to combat the deposits attacked by acidic cleaning compositions and the deposits attacked by alkaline cleaning compositions, but the difficulty in achieving this is self-evident.
  • the patent document US 4 522 738 also solves the problem of removing scale deposits on toilet bowls. It discloses toilet bowl cleaners having inner and outer water-soluble envelopes.
  • the inner envelope contains basic material and the outer envelope contains acidic material which dissolves first and then the inner envelop. The amounts are chosen in that way that the pH changes to release carbon dioxide gas, thereby agitate the bowl water and thus enhance the cleaning process.
  • the British patent document GB 2 000 177 discloses compositions for laundry washing based on an alkali metal carbonate which pH changes from acid to alkaline. There is no mentioning of removing the limescale on hard surfaces.
  • a method of cleaning a hard surface which is subject to deposition by limescale comprising the application to the hard surface of a cleaning composition which comprises reactants which undergo a chemical reaction after exposure to the hard surface to be cleaned, the reaction being such as to produce a delayed change of pH at the hard surface, the composition being initially an alkaline liquid and after an interval becomes an acidic liquid effective in combating limescale.
  • a cleaning composition having the property that on exposure to a hard surface to be cleaned the locus renders acidic or alkaline or neutral, and that after an interval it renders the locus alkaline or neutral (if originally acidic) or acidic or neutral (if originally alkaline) or acidic or alkaline (if originally neutral).
  • composition of any of the aspects may have the property that the hard surface containing the composition is initially an acidic liquid and after an interval becomes an alkaline liquid.
  • composition of any of the aspects may have the property that the locus containing the composition is initially an alkaline liquid and after an interval becomes an acidic liquid.
  • the pH change of at least 2 pH units takes place after an induction period (that is, an interval after exposure of the composition to the locus) of at least 10 seconds, more preferably at least 20 seconds, most preferably at least 60 seconds, and, especially, at least 100 seconds.
  • an induction period that is, an interval after exposure of the composition to the locus
  • the said induction period is not more than 12 hours, preferably not more than 1200 seconds, more preferably not more than 600 seconds, most preferably not more than 400 seconds, and, especially, not more than 300 seconds.
  • a composition of the invention could be a single-pack composition, with the reactants being held in stasis if necessary.
  • the pH change which takes place may be initiated by addition of an agent from which the reactants were previously protected.
  • an agent from which the reactants were previously protected for example, it could be water, or oxygen, or carbon dioxide, or light.
  • the reactants could be kept physically separated from each other prior to their use, as for example in a tablet or dissolvable sachet having two or more zones, which may be layers, portions or encapsulated sections, depending on the type of tablet or sachet, or in a twin-bottle package or twin-tablet package.
  • the key measure is that the reactants are combined only at the time of cleaning.
  • the composition may be provided in a package which emits the composition as a spray, mousse, gel or liquid jet.
  • the package may suitably be a trigger spray or, preferably, an aerosol canister.
  • a spray-emitting package of the composition, especially an aerosol canister, constitutes a further aspect of the invention.
  • a wipable product for example a sponge or cloth, is impregnated with a composition.
  • the composition may be a product for dilution in order to be used, or a product in ready-to-use form.
  • a product When a product is for dilution, it may be a solid, for example a powder or tablet, or a liquid, or a gel.
  • the composition may be provided in packaging giving unit-dose supply of the composition.
  • the composition may be such that the chemical reaction causes a colour change.
  • One or more of the reactants responsible for the change of pH may cause a change of colour, for example on exhaustion, or a separate dye or colorant may be included in the composition, responsive to pH change or to the presence of oxidant species, or reductant species, or temperature change in the case of an exothermic reaction.
  • system could be arranged to effervesce when the reaction takes place, for example by including a bicarbonate in a system which becomes acidic after the induction period.
  • Another method useful in the case of an exothermic reaction employs a fragrance rendered volatile by a temperature rise.
  • cleaning may include: removal of soil deposits: prevention of soiling; bleaching; combating of allergens; and combating of microbes, including by one or more of antiseptic, disinfectant, bactericidal, sporicidal, fungicidal and viricidal action.
  • the composition is antimicrobial.
  • an antimicrobial effect is generated by the reaction, for example by temperature rise when the reaction is exothermic and/or by the pH change at the locus and/or by production of an antimicrobial chemical, in the reaction.
  • an antimicrobial chemical is generated in situ by the reaction which changes the pH, and therefore with the same delay.
  • the antimicrobial chemical may, for example, comprise an iodate, bromate, thiocyanate or chlorate.
  • the composition preferably produces a bleaching effect.
  • a bleaching effect is generated by the reaction, for example by the temperature when the reaction is exothermic and/or by the pH change at the locus and/or by production of a bleaching chemical, in the reaction.
  • a bleaching agent is produced in situ by the reaction which changes the pH, and therefore with the same delay.
  • the composition may include sodium chlorite generating, under acid conditions, sodium hydroxide and chlorine dioxide.
  • both a bleaching agent and an alkaline agent may be generated.
  • composition may contain hydrogen peroxide or a precursor to it as a bleaching agent and/or reactant.
  • the composition may include one or more surfactants.
  • a surfactant used in the present invention may be selected from one or more surfactants which may be anionic, cationic, nonionic or amphoteric (zwitterionic) surface active agents.
  • alkoxylated alcohols particularly alkoxylated fatty alcohols. These include ethoxylated and propoxylated fatty alcohols, as well as ethoxylated and propoxylated alkyl phenols, both having alkyl groups of from 7 to 16, more preferably 8 to 13 carbon chains in length.
  • alkoxylated alcohols examples include certain ethoxylated alcohol compositions presently commercially available from the Shell Oil Company (Houston, TX) under the general trade name NEODOL (trade mark), which are described to be linear alcohol ethoxylates and certain compositions presently commercially available from the Union Carbide Company, (Danbury, CT) under the general trade name TERGITOL (trade mark) which are described to be secondary alcohol ethoxylates.
  • alkoxylated alkyl phenols examples include certain compositions presently commercially available from the Rhône-Poulenc Company (Cranbury, NJ) under the general trade name IGEPAL (trade mark), which are described as octyl and nonyl phenols.
  • non-ionic surfactants that may be used are sorbitan esters of fatty acids, typically of fatty acids having from 10 to 24 carbon atoms, for example sorbitan mono oleate.
  • anionic surface active agents which may be used in the present invention include but are not limited to: alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of one or more of the following compounds: alkyl sulphates, alkyl ether sulphates, alkylamidoether sulphates, alkylaryl polyether sulphates, monoglyceride sulphates, alkylsulphonates, alkylamide sulphonates, alkylarylsulphonates, olefinsulphonates, paraffin sulphonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl saronsinates, acyl isoth
  • anionic surface active agents which may be used include fatty acid salts, including salts of oleic, ricinoleic, palmitic and stearic acids; copra oils or hydrogenated copra oil acid, and acyl lactylates whose acyl group contains 8 to 20 carbon atoms.
  • Amphoteric surfactants which may be used in the present invention including amphoteric betaine surfactant compounds having the following general formula: wherein R is a hydrophobic group which is an alkyl group containing from 10 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, an alkylaryl or arylalkyl group containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or either linkages; each R 1 is an alkyl group containing from 1 to 3 carbon atoms; and R 2 is an alkylene group containing from 1 to 6 carbon atoms.
  • R is a hydrophobic group which is an alkyl group containing from 10 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, an alkylaryl or arylalkyl group containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar
  • One or more such betaine compounds may be included in the compositions of the invention.
  • cationic surfactants which may be used in the present invention include quaternary ammonium compounds and salts thereof, including quaternary ammonium compounds which also have germicidal activity and which may be characterized by the general structural formula: when at least one of R 1 , R 2 , R 3 and R 4 is a hydrophobic, aliphatic, aryl aliphatic or aliphatic aryl group containing from 6 to 26 carbon atoms, and the entire cationic portion of the molecule has a molecular weight of at least 165.
  • the hydrophobic groups may be long-chain alkyl, long-chain alkoxy aryl, long-chain alkyl aryl, halogen-substituted long-chain alkyl aryl, long-chain alkyl phenoxy alkyl or aryl alkyl.
  • the remaining groups on the nitrogen atoms, other than the hydrophobic radicals, are generally hydrocarbon groups usually containing a total of no more than 12 carbon atoms.
  • R 1 , R 2 , R 3 and R 4 may be straight chain or may be branched, but are preferably straight chain, and may include one or more amide or ester linkages.
  • X may be any salt-forming anionic moiety.
  • quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, and N-alkyl pyridinium halides such as N-cetyl pyridinium bromide.
  • alkyl ammonium halides such as cetyl trimethyl ammonium bromide
  • alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide
  • N-alkyl pyridinium halides such as N-cetyl pyridinium bromide.
  • Other suitable types of quaternary ammonium salts include those in which the molecule contains either amide or ester linkages, such as octyl phenoxy ethoxy ethyl dimethyl benzyl
  • Preferred quaternary ammonium compounds which act as germicides and which are useful in the present invention include those which have the structural formula: wherein R 2 and R 3 are the same or different C 8 -C 12 alkyl, or R 2 is C 12 -C 16 alkyl, C 8 -C 18 alkylethoxy, C 8 -C 18 alkylphenolethoxy and R 3 is benzyl, and X is a halide, for example chloride, bromide or iodide, or methosulphate.
  • Alkyl groups R 2 and R 3 may be straight chain or branched, but are preferably substantially linear.
  • a mixture of two or more surface active agents may also be used.
  • Other known surface active agents not particularly described above may also be used.
  • Such surface active agents are described in McCutcheon's Detergents and Emulsifiers, North American Edition, 1982; Kirk-Othmer, Encyclopaedia of Chemical Technology, 3rd Ed., Vol. 22, pp 346-387.
  • compositions of the present invention may include therein one or more organic solvents, such as lower alkyl alcohols, lower alkyl diols or glycol ethers.
  • organic solvents such as lower alkyl alcohols, lower alkyl diols or glycol ethers.
  • Such compounds may function as a cleaning agent of the compositions, and may be especially useful in glass cleaners due to their lack of tendency to smear.
  • the composition is such that after exposure to an locus to be cleaned its temperature rises, preferably caused by the reaction which changes the pH, and therefore with the same delay.
  • the reaction responsible for change in pH is preferably exothermic.
  • the composition may be such that after one pH change the pH may change in the reverse direction.
  • a composition may go from acidic to alkaline and back to to acidic, or from alkaline to acidic and back to alkaline. It is possible that such compositions may undergo further pH changes.
  • Each pH change preferably takes place over an induction period as defined above.
  • Suitable systems may include those described in the following references:
  • the composition may contain components which provide an abrupt pH step.
  • the autocatalytic species for the reaction is H + (or, more rarely, OH - ) and pH steps may occur when a solution of a weak acid is oxidised to provide a strong acid, so that H + concentration increases with the extent of reaction.
  • the chemical composition of a typical pH step system will involve an oxidant and a reductant.
  • the reductant will be the salt of a weak acid and the corresponding oxidant will be a strong acid.
  • a reaction may employ a plurality of oxidants and/or a plurality of reductants.
  • the most widely studied pH step reactions are those typified by the Landolt clock reaction, in which the oxidant is of formula XO n - when X is Cl, Br or I and n is 3 when X is Br or I, and 2, 3 or 4 when X is Cl; and the reductant is SO 3 2- /HSO 3 - .
  • the classic Landolt system employs IO 3 - as oxidant and is SO 3 2- /HSO 3 - as reductant.
  • the reaction is autocatalytic in I - (depending on the second power of the iodide ion concentration) and is a pH step reaction system even in buffered solution. In unbuffered solution, the reaction is also autocatalytic in H + .
  • precursors of hydrogen peroxide include urea hydrogen peroxide (UHP) and a cyclodextrin complexed with an organic peroxy acid, for example as described in EP-A-895777.
  • UHP urea hydrogen peroxide
  • PAP e-phthalimido peroxyhexanoic acid
  • mixed-Landolt system may produce a pH step reaction in which the pH swings from high to low at the end of an induction period, and then back to high pH on a longer timescale.
  • An example of a pH step reaction system starting at low pH and changing to high pH at the end of an induction period involves the reduction of H 2 O 2 (which may be delivered by means of a precursor, as described above) by various multidentate complexes of Fe (II) or Co (II) ions, notably using Fe(CN) 6 4- as the anion species, as described in G. Rabai et al, J.Am.Chem.Soc., 1989, III, p. 3870.
  • Cleaning compositions of the invention may be used, for example, for textile materials, including carpets and clothes. They may be used in dishwasher cleaning compositions and clothes washing compositions.
  • the change of pH may, for example, initiate the dissolution of the coating of a washing tablet or of an insert product contained within a washing tablet, providing in each case delayed release of the contents.
  • a preferred cleaning composition of the present invention is a hard surface cleaner, for cleaning ceramics, glass, stone, plastics and wood; and particularly for cleaning bathroom and kitchen hard surfaces, for example sinks, bowls, toilets, panels, tiles and worktops.
  • a hard surface cleaner for cleaning ceramics, glass, stone, plastics and wood
  • bathroom and kitchen hard surfaces for example sinks, bowls, toilets, panels, tiles and worktops.
  • sinks, bowls, toilets, panels, tiles and worktops for example sinks, bowls, toilets, panels, tiles and worktops.
  • alkaline When alkaline it is particularly effective in combating grease and proteinaceous deposits.
  • Another preferred cleaning composition is adapted for cleaning dentures (normally of polyacrylic material) and is therefore effective in removing staining and/or plaque.
  • compositions are adapted for cleaning lavatory bowls and for this purpose the composition may be packaged in an ITB (In the Bowl) or ITC (In the Cistern) device, preferably in a holder which hangs from the rim of the bowl or cistern.
  • ITB In the Bowl
  • ITC In the Cistern
  • the reactants are preferably liquids kept in separate vessels, or solids formulated in separate tablets (for example compressed powders or granules, or gel blocks) or in one tablet with distinct zones for the different reactants.
  • the reactants may be mixed and only react in use, in which case a single vessel or simple tablet may be used.
  • Another useful cleaning composition is adapted to clean marble surfaces effectively.
  • Such a composition is acidic when applied in order to attack certain stains and soils, but becomes alkaline before any dissolution of the marble can occur. When alkaline it attacks other stains and soils, notably greases.
  • the induction period t ind can be varied between 4 hours and 2 minutes, with t ind being approximately inversely proportional to the initial concentrations of both BrO 3 - and H + and independent of the initial concentration of SO 3 2- .
  • the initial sulphite concentration appears to determine the pH swing, which is typically of the order of 4 to 5 pH units.
  • the reaction occurs for compositions with initial pH values in the range 6.6 to 8.9.
  • the chlorate ion ClO 3 - can also be used as the oxidant in Landolt-type systems.
  • a series of experiments were performed on this system. The reaction does not appear to occur starting from pH values higher than ca. 5.0, so the initial pH was adjusted using concentrated H 2 SO 4 to the range 4.5-5.0 for the experiments reported below. The reaction is strongly exothermic and even for relatively dilute solutions, significant temperature rises (self-heating) occur. The results are set out in Table 6 and 7 below.
  • Table 9 above shows how the induction period changes depending on whether the reactants are used in solution or dry powder form.
  • the induction period was increased for the dry powder experiments, but this increase was very small and in most cases only increases the induction time by a few seconds. There was no noticeable difference in the temperature rise and initial and final pH between the dry powder and solution experiments. A powder system was accordingly shown to be of possible value in the present invention.
  • bromate-sulphite In a bromate-sulphite system the co-addition of surfactants typically used in household cleaning compositions was studied. A set of initial concentrations were chosen (bromate 0.5M, sulphite 0.65M and bisulphite 0.018M) and a selection of surfactants were added, as identified in Table 11 below.
  • Sodium lauryl sulphate is a well-known anionic surfactant.
  • Polytergent® SL-62 is a non-ionic surfactant, a mixture of ethoxylated and propoxylated fatty alcohols, from BASF.
  • the glycol ether was DOWANOL® DPnB glycol ether.
  • Empigen® BAC 50 is a cationic surfactant, a benzalkonium chloride, more specifically C 10-16 (predominantly C 12-14 ) alkyl dimethyl benzylammonium chloride.
  • Tables 12 and 13 show the results from the experiments In each case the results are the mean results of three replicates.
  • Table 12 shows the results for the initial concentrations bromate 0.5M, sulphite 0.65M and bisulphite 0.018M and
  • Table 13 shows the results for the initial concentrations bromate 0.7M, sulphite 0.5M and bisulphite 0.018M.
  • the test method for Sample 2 was as follows: 1ml bacterial suspension (10 7 cfu/ml) of the selected bacterium was transferred to a flask containing 1ml of a 3% BSA suspension. The culture/ soil mix was vortex mixed and then shaken on an orbital shaker for 2 minutes. To the culture/ soil mix was added 8ml sterile hard water. Mixing was continued for another minute. Without interruption of the shaking, the chemical compounds of the appropriate samples were added to the flask in powder form, in amounts calculated to give the molarities mentioned above. 5 minutes after addition of the sample, shaking was stopped and a 1ml aliquot of the test mixture was transferred to 9.0ml neutralising medium.
  • test sample 1 was serially diluted and used to prepare pour plates which were subsequently incubated at 36°C for 48 hours before enumerating surviving bacteria. As an inactive control, testing was repeated without the addition of the test sample.
  • the test method for Sample 1 was similar but as noted above did not employ hard water or BSA.
  • Test organism Median ME values (Sample 1) Water (control) S.aureus >5.7 0.1 E.coli >5.4 0.1
  • Median ME values (n 3) from further testing
  • Test organism Median ME values S.aureus 5.3 E.coli 5.4 P.aeruginosa >5.2
  • a hard surface cleaning composition has the following composition.
  • TERGITOL® secondary alcohol 0.6% w/w ethoxylate Ethylene glycol-n-butyl ether (non-ionic surfactant) Fragrance 0.2% w/w Colour trace H 2 O 2 0.1% w/w Na 2 S 2 O 3 0.16% w/w Na 2 SO 3 0.05% w/w H 2 SO 4 0.005% w/w
  • a hard surface cleaner has the following composition: Ethoxylated fatty alcohol (C 12-14 ;3EO) 1% w/w (non-ionic surfactant) Ethylene glycol 5% w/w Fragrance 0.1% w/w Colour trace NaIO 4 0.43% w/w Na 2 S 2 O 3 0.16% w/w Na 2 SO 3 0.06% w/w H 2 SO 4 0.01% w/w Butane (propellant) 18% w/w Deionised water to 100% w/w
  • the components were mixed and loaded into spray canisters with exclusion of air. Only on spraying a surface with this composition, for cleaning, does the pH step reaction start.

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Claims (11)

  1. Verfahren zur Reinigung einer harten Oberfläche, auf welcher sich Kalk ablagert, wobei das Verfahren das Aufbringen einer Reinigungszusammensetzung, die Reaktanten umfasst, die sich nach Einwirkung auf die harte Oberfläche einer chemischen Reaktion unterziehen, auf die harte Oberfläche umfasst, wobei die Reaktion derart ist, dass eine verzögerte Änderung des pH-Werts auf der harten Oberfläche erzeugt wird, indem die Zusammensetzung anfänglich eine alkalische Flüssigkeit ist und nach einem Zeitraum zu einer beim Bekämpfen von Kalk wirksamen sauren Flüssigkeit wird.
  2. Verfahren nach Anspruch 1, wobei die Zusammensetzung die Eigenschaft aufweist, dass die Zusammensetzung nach Einwirkung auf die harte Oberfläche eine verzögerte Änderung des pH-Werts von mindestens 2 pH-Einheiten auf der harten Oberfläche erzeugt.
  3. Verfahren nach Anspruch 1 oder 2, wobei die Zusammensetzung ein Oxidationsmittel, ausgewählt aus einer Peroxyverbindung und einer in alkalischen Lösungen stabilen oxidierenden Metallverbindung, und ein Reduktionsmittel, ausgewählt aus einem Oxyanion oder S-S-Bindungen enthaltendem Schwefel und einer Verbindung, die im Wesentlichen basischer als ihr oxidierter Gegenpart ist, umfasst.
  4. Verfahren nach Anspruch 3, wobei das Oxidationsmittel ausgewählt ist aus der Spezies BrO3 - IO3 -, ClO3 -, ClO2 -, S2O8 2-, ClO2, [Fe(CN)6]3- und H2O2 oder einer Vorstufe dazu, und das Reduktionsmittel ausgewählt ist aus der Spezies S2O3 2-, S4O6 2-, S2O6 2-, SO3 2- und N2H5 +, wobei das Oxidationsmittel und das Reduktionsmittel gemeinsam an pH-Schwankungen erzeugenden Reaktionen teilnehmen.
  5. Verfahren nach einem der vorangehenden Ansprüche, wobei die Zusammensetzung eine antimikrobielle Wirkung auf der harten Oberfläche erzeugt.
  6. Verfahren nach einem der vorangehenden Ansprüche, wobei die Zusammensetzung eine Bleichwirkung auf der harten Oberfläche erzeugt.
  7. Verfahren nach einem der vorangehenden Ansprüche, wobei eine Temperaturerhöhung durch die Reaktanten auf der harten Oberfläche erzeugt wird.
  8. Verfahren nach einem der vorangehenden Ansprüche, wobei die Zusammensetzung derart ist, dass sich die pH-Änderung durch eine Farb- oder Geruchsänderung oder durch Sprudeln zeigt.
  9. Verfahren nach einem der vorangehenden Ansprüche, umfassend ein oberflächenaktives Mittel.
  10. Verfahren nach einem der vorangehenden Ansprüche, wobei die Zusammensetzung unter Ausschluss von Sauerstoff und/oder Wasser und/oder Kohlendioxid und/oder Licht verpackt wird, wie es zum Verhindern einer pH-Änderung vor der Verwendungseinwirkung erforderlich ist.
  11. Verfahren nach einem der vorangehenden Ansprüche, wobei die harte Oberfläche eine wässrige Umgebung ist und das Verfahren die Verdünnung der Reinigungszusammensetzung in der wässrigen Umgebung umfasst.
EP01954112A 2000-07-18 2001-07-17 Reinigungsverfahren harter oberflächen Revoked EP1303583B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB0017549.7A GB0017549D0 (en) 2000-07-18 2000-07-18 Improvements in or relating to chemical compositions and their use
GB0017549 2000-07-18
PCT/GB2001/003136 WO2002006434A1 (en) 2000-07-18 2001-07-17 Cleaning compositions and their use

Publications (2)

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EP1303583A1 EP1303583A1 (de) 2003-04-23
EP1303583B1 true EP1303583B1 (de) 2005-10-26

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EP (1) EP1303583B1 (de)
AR (1) AR029847A1 (de)
AT (1) ATE307874T1 (de)
AU (1) AU2001276461A1 (de)
DE (1) DE60114422T2 (de)
ES (1) ES2248360T3 (de)
GB (2) GB0017549D0 (de)
WO (1) WO2002006434A1 (de)

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US7883640B2 (en) * 2004-11-10 2011-02-08 The United States Of America As Represented By The Secretary Of The Army Chemical combination for generation of disinfectant and heat
WO2009105232A1 (en) * 2008-02-21 2009-08-27 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US9481854B2 (en) 2008-02-21 2016-11-01 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US9410111B2 (en) 2008-02-21 2016-08-09 S.C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US8980813B2 (en) 2008-02-21 2015-03-17 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits
US8993502B2 (en) 2008-02-21 2015-03-31 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits
BRPI0908179A2 (pt) * 2008-02-21 2015-11-24 Johnson & Son Inc S C composição de limpeza possuindo alta auto-adesão e provendo benefícios residuais
US8143206B2 (en) * 2008-02-21 2012-03-27 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US9103038B2 (en) * 2012-05-29 2015-08-11 Ecolab Usa Inc. Acidic compositions including reducing agents for scale and decolorization of metal stains
ES2967798T3 (es) 2017-06-22 2024-05-03 Ecolab Usa Inc Blanqueo utilizando a¿cido peroxfo¿rmico y un catalizador de oxi¿geno

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AR029847A1 (es) 2003-07-16
US20040072710A1 (en) 2004-04-15
AU2001276461A1 (en) 2002-01-30
DE60114422T2 (de) 2006-07-27
EP1303583A1 (de) 2003-04-23
GB2367832B (en) 2003-03-19
ES2248360T3 (es) 2006-03-16
GB2367832A (en) 2002-04-17
WO2002006434A1 (en) 2002-01-24
GB0117274D0 (en) 2001-09-05
ATE307874T1 (de) 2005-11-15
GB0017549D0 (en) 2000-09-06
DE60114422D1 (de) 2005-12-01

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